JPS5982372A - Hexahydropyridazinecarboxylic acid derivatives and herbicides containing them as active ingredients - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X is Cl or Br; Y is O or S; R1 is lower alkyl, lower alkenyl or lower alkynyl; R2 is lower alkyl). EXAMPLE:Ethyl 2-[4-chloro-2-fluoro-5-(1-methylethoxy)phenylaminothioxomethyl]- 3,4,5,6-tetrahydro-1(2H)-pyridazinecarboxylate. USE:Useful as a herbicide, capable of exhibiting herbicidal effects on broadleaf weeds, e.g. sunflower, gramineous weeds, e.g. Deccan grass, by the foliar and soil treatment, and having effects on gramineous weeds, e.g. barnyard grass, and broadleaf weeds, e.g. false pimpernel, without phytotoxicity to main crops. PROCESS:A phenyliso(thio)cyanate derivative of formula II is reacted with a compound of formula III in a solvent in the presence of a catalytic amount of a dehydrohalogenating agent to afford the aimed compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein or a chlorine atom or a bromine atom is replaced by YiI:1.
an oxygen atom or a sulfur atom, R1 is a lower alkyl group,
A lower alkenyl group or a lower alkynyl group, a tetrahydropyridazine carboxylic acid moiety represented by f (2 represents a lower alkyl group) (hereinafter referred to as the compound of the present invention), its production method, and its active ingredient. This article relates to a violet removal agent.

Certain tetrahydropyridazine derivatives, such as ethyl-β-(chloro-3-fluorophenylaminothioxomethyl)-3,'1.3-,
The use of tetraLdo0-/()-()-pyridazine-lupoxyle-1 as an active ingredient in herbicides is described in JP-A-7G3. However, these compounds are one of the active ingredients of herbicides and must be
“But it cannot always be said to be sufficient.

The compound of the present invention can be used to treat fΦ, which is a problem in field grass treatment and vehicle stopping treatment. Miscellaneous-1 For example, freckles,
Japanese knotweed, purslane, white herb, blueberry, Japanese radish, Japanese radish, shepherd's purse, American hornwort, Ebisugusa, Japanese commonweed, American goldenrod, field pansy, American morning glory, Maruba morning glory, St. convolvulus, Styxweed, Japanese radish, Japanese morning glory , Japanese Physalis, Japanese Physalis, Japanese Physalis, Japanese Physalis, Sunflower,
Broad-leaved weeds such as dogberry and corn marigold, Japanese barnyard grass, Japanese barnyard grass, foxtail grass, grasshopper, black grass, oat, oat, and
It does not cause any harmful chemical damage to grass weeds such as grass weeds and major crops such as wheat, soybeans, cotton, and rice.

The compounds of the present invention can be used in water [U. It has a herbicidal effect on paddy field weeds such as Cyperaceae, Cyperaceae, Cyperaceae, etc.
Moreover, it does not cause any serious chemical damage to rice.

The compound of the present invention can be used in rice fields, fields, orchards, pastures, and lawns.
b. It can be used as an active ingredient in forest or non-agricultural herbicides.

The compound of the present invention is a phenyliso(thio)cyanate derivative represented by the general formula [wherein X, Y and 1 (1 represents the same meaning as above]) and/
, θ to 8 equivalents of the general formula [wherein R2&j represent lower alkyl ordination groups]. ] 3, 41, 3;, 1. -tetrahydro=/-(,2H
)-carboxylate in a detergent in the presence of a catalytically scavenging dehydrohalogenating agent for θ°C to /θθ°C1/hr to yg hours.

For polishing, aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benbin, toluene, and xylene, and halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene are used. Hydrocarbons, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone,
Water, etc. or a mixture thereof.

Dehydrohalogenation agents include pyridine, triethylamine, N, 1. Examples include organic bases such as J-dienalaniline.

After the reaction is complete, carry out the usual post-treatment, and if necessary, add chlorine 7.
Purify by tography, distillation, recrystallization, etc.

Next, production examples of the compounds of the present invention will be shown.

Fruit production example/ (Production of the compound of the present invention) q-chloro-β
-Fluoro-5-(/-methylethoxy)phenylthiocyanate 2.8g, 2-ethoxycarbonyl-3
,q.

3-7 Add a few drops of triethylamine to a mixture of 3-7-tetrahydro-(/H,2H)-pyridazine/, Pnia, and 3 ml of toluene, and leave at -5°C overnight. I hit l. Water was added to toluene; ψ'l was separated by -5), washed with water, dried, and concentrated. What’s left? It was purified using a silica gel column to obtain ethyl 2-[terchloro-ρ-fluoro-3-(,/-methylethoxy)phenylaminona-3xomethyl]-3,
Ge.

S,6-titrahydro/(,2H)-viridashi:/
ノJ Lubokin L/-) t;ノ, (-011D
/ -553<'This is how it is 7.1'
Here are some of the compounds and products of the present invention that can be done! / Shown in the table, / Table General formula When producing the compound of the present invention, the basic general formula [n]
Phenyl, iso(thio)cyanate derivative d General formula] [In the formula, X, , Y and R11J have the same meanings as above. ) It can be produced by reacting the S form of aniline a represented by the following formula with phosgene or thiophosgene in an amount of 0 to /θθ equivalent in a solvent from room temperature to the boiling point of the solvent for qg hours/hour.

Examples of solvents include benzene, toluene, tetrahydrofuran, ethyl acetate, and q-dioxane.

After the reaction is completed, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, distillation, recrystallization, etc.

Next, a production example of the phenyliso(thio)cyanate derivative of the general formula [■] will be shown.

Production example: Cocochlorine-fluoro-5-(/-methylethoxy)-7 diton 3θ1 was dissolved in toluene/θθm/′,
Phosgene was added to the /M l-toluene solution and the reaction system was refluxed until it became homogeneous.

After concentrating under reduced pressure, the residue was distilled to obtain 2-chlorofluoro-fluoro(/-methylethoxy)-7enyl isocyanate of ρotsu7. bp9θ~9/”C
, 73rmHF, , mp 3 /, ~37°C When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid phase, a surfactant, and other formulation auxiliaries to form an emulsion or an irrigation agent. Formulation J- for agents, suspensions, granules, etc.
Ru.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of θ, /~9j, preferably θ0.2~.

The 4F4 bodies include kaolin clay, attapulsimite clay, bentonite, acid clay, pyrophyllite,
There are fine powders or granules such as talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrated silicon oxide, and liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, isopropanol, and ethylene glycol. , alcohols such as cellosolve, ketones such as acetone, cyclohexanone, isophorone, vegetable oils such as oil, cottonseed oil, dimethyl sulfoxide, acetonitrile,
There is water etc.

0 for surfactants used for emulsification, dispersion, wet carbon, etc.
, anionic surfactants such as alkyl sulfate salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl 7-aryl ether phosphate salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryls, etc. ether,
There are nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxysorbitan fatty acid ester.

Auxiliary substances for formulation include lignin sulfone t-t*, alginic acid Jg, polyvinyl alcohol, gum arabic, C
! Examples include MG (carboxymethylcellulose) and PAP (isopropyl acid phosphate). , Next, a formulation example is shown. In addition, the present invention compound il'J' No. 7
Indicated by compound number in the table. The 1-Ho section is shown in the section.

Formulation Example: 50 parts of the compound of the present invention, 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 95 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain an irrigation agent.

Formulation Example 1 6.70 parts of the compound of the present invention, 77 parts of polyoxyethylene styrylphenyl ether, 199,230 parts of calcium dodecylbenzenesulfonate, and θ part of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 3 Two parts of the compound of the present invention, one part of synthetic hydrous silicon oxide, one part of calcium lignosulfonate, one part of bentonite 3θ, and one part of kaolin clay A3 were thoroughly ground and mixed, and after adding water and kneading well, Granulate and dry to obtain granules.

Formulation Example Compound of the present invention/θ, 28 parts, polyoxyethylene sorbitan monooleate Jf? A suspension is obtained by mixing S, 53 parts of CMC, and 69 parts of water and wet-pulverizing the active ingredient until the particle size becomes 3 microns or less.

These preparations are diluted with 1-1: Irrigation water, etc.
Stem #-process cape or soil treatment. For soil treatment, spray the preparation on the soil surface (if necessary, spray 1" after 10")
Mixes with 3j+. ) or on the soil.

By using Muff ζ in combination with other herbicides, it is expected that the herbicidal efficacy will be enhanced. In addition, insecticides, acaricides,
It can also be used in combination with nematicides, fungicides, plant growth regulators, IJ[414, and Shihoku improver Tatami.

When the compound of the present invention is used as an active ingredient of a herbicide, its Mn information is generally θ, θ/g~/θθ
y1 The preferred size is θ, α2 ~ gθ2, and the emulsion, hydrating agent, opening method 1 agent, etc. is / liter / θ liter per / area (If necessary, aim ゛, spraying aids such as spreading agent It is applied by diluting it with water (added with the agent), and it is applied as it is without diluting Q-man such as granules.

Test examples show that fq of the above-mentioned surfactants, polyoxyethylene resin acid (ester), lignin sulfonate, abietate, and dinaphthylmeth are useful as spreading agents. It is indicated by the compound number in Table 1, and the compound date used for comparison is indicated by the compound symbol in Table 2.
of.

The herbicidal efficacy against weeds and crops is determined by visual observation of the degree of germination and growth inhibition of the test plants during the survey, and the degree of inhibition of germination and growth of the test plants at the time of the survey is determined. If the test seed is dead or its growth is completely inhibited, it is evaluated as "5", and evaluated in 6 stages from θ to j, and is indicated by θ, /, β, 3, ri, and j.

Test example / Upland soil mixing treatment test Diameter / θcm, depth 10eyn 1 circle 1 type plasti 7
Fill the kubonto with field soil, sow barnyard grass, oats, Japanese morning glory, and Japanese strawberry, and cover with soil. The test compound made into an emulsion according to Formulation Example 2 was diluted with water equivalent to /θ liter per area, and then sprinkled on the soil surface with a dense container at a depth of 111'(111') at a depth of 111'. After spraying, the plants were grown indoors for 18 days and their herbicidal efficacy was investigated.The results are shown in Table 3.

Table 3 Test Example - Upland Grass Treatment Test A cylindrical plastic pot with a diameter of 70 mm and a depth of 70 mm was filled with upland soil, and barnyard grass, oats, radish, and Japanese radish were sown and grown in a greenhouse for 10 days. Then, Formulation Example J
The test compound made into an emulsion according to the method was diluted with water containing a spreading agent equivalent to /are /θ liter, and the predetermined area was sprayed on the foliage from above the plant using a small sprayer. 20 days after spraying
The plants were grown in a greenhouse for 1 day and their herbicidal efficacy was evaluated. The results are shown in the 41st paper.Paddy field soil treatment, test diameter δ゛, depth/, 2-ounce cylindrical plastic pots were filled with paddy soil, and Japanese millet and broad-leaf stage rice were transplanted. , grew up in Wenning. 6 days later (early stage of emergence of each rush)
The test compound was made into an emulsion according to the formulation example-/Bot 4.
) or diluted with 1 ml of water and dripped onto the water surface in the designated area. λθ days after dropping i! It was grown indoors and its herbicidal efficacy was investigated. The results are shown in Table 3.

a・(Experiment 15'l llJ, llIl Land mixing treatment test 1?i 4;73 J , American hornwort,
7Iif 1. Invite Japanese fir tree, Ichibi, Maruba morning glory, and Buckwheat 7Iif 1. ,,/~, 2 on thickness.

According to the formulation example
It was sprayed live on the soil surface with all the small fIλ.
The surface layer of the soil was thoroughly mixed. 1 ton of corn, wheat, cotton, and dice seeds
It was buried to a depth of 2 on.

After spraying, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated.

The results are shown in Table 6.

Test example j Field soil treatment test Area: 33 x 23 cd, depth // Filled with field soil in a vat, corn, wheat, American hornwort,
Japanese fir tree, Japanese fir tree, Japanese morning glory, blue-green algae, and Japanese algae were sown and grown for several days. After that, the formulation example]
The test compound was made into an emulsion according to the above method, diluted with j liters of water containing a spreading agent per area, and a predetermined amount of the compound was sprayed uniformly over the entire stem and foliage from the top of the plant using a small sprayer. At this time, the growth of each plant differs depending on the grass species, but the height of the plant at the / ~ leaf stage is... ~/,! It was Kushi. The herbicidal efficacy was investigated 30 days after spraying. The results are shown in Table 7. This test was conducted in a greenhouse throughout the entire period.

Claims (1)

[Claims] (1) General formula [In the formula, or a chlorine atom or a bromine atom, Y is an oxygen atom or a sulfur atom, R1 is a lower furkyl group, a lower alkenyl group, or a lower alkynyl group, "2 is a lower alkyl group (J ) general formula [wherein, X represents a bromine atom after removing a chlorine atom, Y represents an oxygen atom or a sulfur atom, and R1 represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group]. ) A general method characterized by reacting a cyanate derivative with 3,S,6-detrahydro/(,2H)-pyridazinecarboxylate represented by the general formula [wherein R2 represents a lower alkyl group]. A method for producing a tetrahydropyridazine carboxylic acid derivative represented by the formula [wherein, X, Y, R1 and R2 have the same meanings as above]. [wherein, X is a chlorine atom or a bromine atom, and Y is an oxygen atom] #MP or a sulfur atom, R1 represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, and R2 represents a lower alkyl group.] A weed killer characterized by containing a tetrahydropyridazine carboxylic acid derivative represented by the following as an active ingredient. agent.